CN115315540A

CN115315540A - Conversion coating for a tank containing a hydrogen sulfide generating liquid

Info

Publication number: CN115315540A
Application number: CN202180022086.6A
Authority: CN
Inventors: S·贝泽尔; V·S·帕格诺蒂; M·麦克米伦
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2020-03-24
Filing date: 2021-03-23
Publication date: 2022-11-08
Also published as: EP4127263A1; US20230107608A1; WO2021195152A1

Abstract

The present disclosure relates to the use of a conversion coating to reduce or prevent the production of hydrogen sulfide in a tank containing a hydrogen sulfide generating liquid (such as wine). The present disclosure also relates to metal cans that include a conversion coating deposited on at least a portion of an inner surface of the metal can, a film-forming layer deposited on such conversion coating, and a hydrogen sulfide generating liquid deposited within the metal can.

Description

Conversion coating for a tank containing a hydrogen sulfide generating liquid

Technical Field

The present disclosure relates generally to metal cans having a hydrogen sulfide liquid deposited thereon, wherein the metal can includes a conversion coating deposited on at least a portion of an interior surface thereof and a film-forming layer.

Background

Coatings are applied to many substrates to provide protective and/or decorative qualities. Sulfur dioxide and/or the like, such as metabisulfite, is added to some liquids to stabilize the liquid,preventing the growth of harmful bacteria and yeast. Other liquids may produce sulfur dioxide through metabolism of sulfur-containing amino acids or other organic processes. However, sulfur dioxide and/or the like may lead to the production of Volatile Sulfur Compounds (VSC), such as hydrogen sulfide and H ₂ S, the corrosion of the container, the generation of smelly eggs, the pollution of liquid in the metal tank and the like are caused. Accordingly, there is a need for tanks that package such liquids while reducing and/or eliminating hydrogen sulfide and other VSC production.

Disclosure of Invention

The present disclosure relates to a metal can comprising a conversion coating deposited on at least a portion of an inner surface of the metal can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus-containing monomeric subunit m2; a film-forming layer deposited on at least a portion of the conversion coating; and a hydrogen sulfide generation liquid in the metal tank.

Also disclosed is a metallic can comprising a conversion coating deposited on at least a portion of an inner surface of the metallic can, wherein the conversion coating is deposited from a conversion coating composition comprising a lanthanide, a group VIB, a group IIIB, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally a phosphorus-free monomeric subunit m2; a film-forming layer deposited on at least a portion of the conversion coating; and a hydrogen sulfide generation liquid in the metal tank.

The present disclosure also provides a method of packaging a hydrogen sulfide-producing liquid in a metal can, the method comprising depositing the hydrogen sulfide-producing liquid in the metal can, wherein the metal can comprises a conversion coating deposited on at least a portion of an inner surface of the metal can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomer subunit m1 and optionally a phosphorus-free monomer subunit m2; and a film-forming layer deposited on at least a portion of the conversion coating.

The present disclosure also contemplates a metal can comprising a conversion coating deposited on at least a portion of an inner surface of the metal can, the conversion coating comprising a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally a phosphorus-free monomeric subunit m2; a film-forming layer deposited on at least a portion of the conversion coating; and a hydrogen sulfide generating liquid deposited in the metal can, wherein the hydrogen sulfide concentration of the hydrogen sulfide generating liquid as measured with a gas detection tube is less than 35ppb at least two months after the metal can is sealed.

Detailed Description

In accordance with the present disclosure, there is provided herein a metal can comprising, consisting essentially of, or consisting of: a conversion coating deposited on at least a portion of the inner surface of the metallic can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2; a film-forming layer deposited on at least a portion of the conversion coating; and a hydrogen sulfide generating liquid deposited in the metal can.

As used herein, "conversion coating," composition, and similar terms refer to a self-supporting inorganic continuous or semi-continuous layer formed on the surface of a metallic can via a chemical process of reacting with the surface of the metallic can. "continuous layer" refers to an unbroken layer of conversion coating formed over the entire substrate surface. "semi-continuous layer" means a broken layer, that is, a layer that is discontinuous over its entire surface.

Without being bound by theory, it is believed that the conversion coating disclosed herein reduces oxidation of the metal substrate of the can by the hydrogen sulfide generating liquid, thereby preventing and/or reducing subsequent reduction of sulfur dioxide and other sulfides in the hydrogen sulfide generating liquid. It is believed that inhibiting such reaction between the metal within the canister and free sulfur dioxide in the hydrogen sulfide generating liquid reduces and/or prevents corrosion of the metal canister and contamination of the hydrogen sulfide generating liquid, such as (but not limited to) wine deposited therein.

The term "metal can" encompasses any type of metal can, container, or any type of receptacle or portion thereof that is sealed by a content manufacturer (e.g., a food and/or beverage manufacturer) to minimize or eliminate spoilage of the content until a consumer opens such metal can. The can may comprise "two-piece cans" and "three-piece cans" as well as thin-walled drawn one-piece cans; such unitary cans are commonly used for aerosol products. The metal can may be a food and/or beverage can. The canister may be a one-piece aerosol canister and/or a tube. Suitable examples of integral aerosol cans and/or tubes include, but are not limited to, deodorants and hair spray containers. The metal can may be a metal can bottle.

The metal can may be made of any suitable material. Suitably, the metal can comprises a metal substrate, a metal alloy substrate and/or a substrate that has been metallised, such as nickel plated plastic. Suitable examples include, but are not limited to, the following: steel, tinplate pretreated with protective materials such as chromium, titanium, titanate, or aluminum, tin Free Steel (TFS), galvanized steel such as, for example, electro-galvanized steel, and the like, aluminum alloys, and combinations thereof.

The metal or metal alloy may comprise or may be steel, aluminium, magnesium and/or alloys thereof. For example, the steel substrate may be cold rolled steel, hot rolled steel, electro galvanized steel, and/or hot dip galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX or 7XXX series, as well as aluminum-clad alloys, may also be used as substrates. The aluminum alloy may include 0.01 wt.% copper to 10 wt.% copper. The treated aluminum alloy may also comprise castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g., A356.0). For example, the metal can may comprise an aluminum alloy of the 3XXX series, such as an aluminum alloy of the AA3104, AA3003, AA3004, AA3005, and/or AA5XXX series. AZ31B, AZ C, AM B or EV31A series magnesium alloy may also be used as the base material. Additionally, the substrate may comprise a non-metallic conductive material comprising a composite material such as, for example, a material comprising carbon fibers or conductive carbon. The substrate may also comprise other suitable non-ferrous metals such as titanium or copper, as well as alloys of these materials.

Those skilled in the art will appreciate that the body of the metal can and the can end may be made of the same or different materials, such as the same or different metals. Suitably, the body of the metal can and the can end may be made of the same material, such as the same metal.

The can body and/or can end may be made from a coil of sheet metal. Suitably, at least the can end may be made from a coil of sheet metal. Suitably, the conversion coating composition of the present invention may be applied to a coiled metal sheet, such as a coiled metal sheet from which can ends are made ("can end sheet").

The conversion coating composition may be applied to the can end panel prior to cutting and stamping the can end from the coiled metal panel. Can ends having a score line may be "easy open" can ends, sometimes referred to as "easy open ends" or even "EOE". Suitably, the score line is applied to the can end after the can end has been stamped from a roll of sheet metal. Once formed, the can end is suitably attached to the can body. The can end may be attached to the can body by any suitable method. Suitably, the can end may be attached to the can body by edge rolling.

The coating composition may be applied to substantially all or part of the inner surface of the can end. For example, the coating composition may be applied to at least a portion of the inner surface of the can end that exceeds at least a portion of the score line. The conversion coating composition may be applied to at least a portion of the inner surface of the can end beyond a partial score or to the inner surface of the can end beyond a full score. Suitably, the coating composition may be applied to substantially all of the inner surface of the can end.

As described above, the metal can includes a conversion coating deposited on at least a portion of an inner surface of the metal can, wherein the conversion coating includes a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer including a phosphorus-containing monomer subunit m1 and optionally no phosphorus-containing monomer subunit m2. The conversion coating may be deposited on at least a portion of the inner surface of the can body and/or can end of the metal can.

As described in detail below, the conversion coating may be made of a conversion composition that includes, consists essentially of, or consists of: a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus-containing monomeric subunit m2.

The lanthanide may include cerium, praseodymium, terbium and/or alloys thereof. The group IIIB metal may include yttrium, scandium, and/or alloys thereof. The group IVB metal may include zirconium, titanium, hafnium and/or alloys thereof. The group VIB metals can include chromium (III), chromium (VI), molybdenum, and combinations thereof.

The conversion coating can comprise a homopolymer or copolymer comprising a phosphorus-containing monomer subunit m1 and optionally a non-phosphorus-containing monomer subunit m2. Any of the monomeric subunits m1 and m2 described herein can be used in the conversion coating. For example, when the metal can comprises aluminum and/or an aluminum alloy, the conversion coating is formed when aluminum oxide forms an ester at the surface with a phosphate or phosphoric acid group (Al-O-P bond) of a homopolymer or copolymer comprising the phosphorus-containing monomer subunit m1 and optionally the phosphorus-free monomer subunit m2.

The copolymer may be a dimer, trimer or high polymer. The homopolymers or copolymers may be statistical or block homopolymers or copolymers, and may be prepared by free-radical continuous or batchwise polymerization.

As used herein, the terms "homopolymer" and "homopolymer comprising monomer subunit m1," when used in reference to a homopolymer disclosed herein, refer to a homopolymer resulting from the polymerization of one monomer m1, wherein the homopolymer does not comprise any other monomer subunits.

As used herein, the term "copolymer" when used in the present invention refers to a dimer or high copolymer of at least one monomer m1 polymerized with at least one monomer m2 or at least two monomers m1. For clarity, "copolymer" includes dimers, trimers and higher copolymers.

As used herein, the term "dimer" when used in the copolymers of the present invention refers to a copolymer of one monomer m1 polymerized with one monomer m2 or two monomers m1.

As used herein, the term "terpolymer" when used in the present invention refers to a copolymer polymerized from three monomer subunit types, wherein at least one monomer is m1.

Suitable examples of phosphorus-containing monomeric subunits m1 comprise organophosphorus compounds which contain phosphates, phosphates and/or phosphates, phosphonic acids, phosphonates and/or phosphinic acids, phosphinates and/or phosphinates. Examples include, but are not limited to, vinyl phosphonic acid, dimethyl vinyl phosphonate, diethyl vinyl phosphonate, other dialkyl vinyl phosphonates, dimethyl phosphonate maleate, diethyl phosphonate maleate, phosphate, phosphonate, or phosphinate substituted methacrylate or acrylate monomers, phosphate, phosphonate, or phosphinate substituted acrylamide monomers, or other monomers containing phosphorus containing substituents and polymerizable bonds.

As used herein, the term "(meth) acrylic acid" when used in reference to a monomeric unit refers to acrylic acid and/or methacrylic acid subunits.

As used herein, the term "(meth) acrylate" refers to an acrylate, a methacrylate, or a mixture of an acrylate and a methacrylate.

Suitable examples of phosphorus-containing monomeric subunits m1 include those comprising the structure of formula I:

wherein R is ₁ And R ₂ Including hydrogen, cationic, alkyl, aryl or phosphate groups, R ₃ Comprising an organic linking group terminating in an atom covalently bonded to an atom in the backbone of the addition polymer. The organic linking group may comprise at least one carbon atom and may comprise further functional groups such as, for example, one or more ether, amine or hydroxyl functional groups, among which at least a portion of the organic linking group, if at least two ether groups are present, may comprise a polyether. The organic linking group may comprise an organic chain, and the organic chain may terminate at carbon atoms on either side of the chain.

Other suitable examples of phosphorus-containing monomeric subunits m1 include those comprising the structure of formula II:

wherein R is ₁ And R ₂ Comprising hydrogen, a cation, an alkyl group, an aryl group or a phosphate group, wherein R ₁ And R ₂ May be the same or different, and wherein R ₃ Comprising an organic linking group terminated with an atom covalently bonded to a carbon atom in the backbone of the addition polymer. The organic linking group may comprise at least one carbon atom and may comprise further functional groups such as, for example, one or more ether, amine or hydroxyl functional groups, among which at least a portion of the organic linking group, if at least two ether groups are present, may comprise a polyether. The organic linking group may comprise an organic chain, and the organic chain may terminate at carbon atoms on either side of the chain.

Further suitable examples of phosphorus-containing monomeric subunits m1 include those comprising the structure of formula III:

wherein R is ₁ Comprising hydrogen, a cation, an alkyl, an aryl or a phosphate group, R ₂ Including hydrogen, alkyl or aryl radicals, R ₃ Comprising an organic linking group terminated with an atom covalently bonded to an atom in the backbone of the addition polymer. The organic linking group may comprise at least one carbon atom and may comprise further functional groups such as, for example, one or more ether, amine or hydroxyl functional groups, among which at least a portion of the organic linking group may comprise a polyether if at least two ether groups are present. The organic linking group may comprise an organic chain, and the organic chain may terminate at carbon atoms on either side of the chain.

Further suitable examples of phosphorus-containing monomeric subunits m1 include those comprising a polymerizable double bond and a phosphorus-containing functional group, such as phosphine, phosphine oxide, phosphonium salt or phosphoric acid amide.

The monomer subunit m2 may be any phosphorus-free monomer capable of copolymerizing with the monomer subunit m1. For example, m2 may be a carboxylic acid or anhydride containing monomeric subunit.

The monomeric subunit m2 may be an acid or anhydride functional ethylenically unsaturated monomer. Suitable examples of the monomer subunit m2 include methacrylic acid, acrylic acid, maleic acid or anhydride thereof, fumaric acid, itaconic acid or anhydride thereof.

The monomeric subunit m2 may also be a (meth) acrylate. Suitable examples of the (meth) acrylate monomer subunit m2 include alkyl esters of (meth) acrylic acid. Non-limiting examples of the alkyl ester of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Other suitable examples of monomeric subunits m2 include (meth) acrylamides, such as N-isopropylacrylamide, maleates, fumarates or itaconates, vinyl monomers, such as styrenes, styrene sulfonic acid, vinyl ethers, or other monomers containing a polymerizable double bond, such as N-vinylpyrrolidone.

In one example, the copolymers disclosed herein can comprise a dimer comprising subunits m1 and m2 and having the structure of formula IV:

wherein x varies from greater than 5mol% to 100mol% and y varies from 0mol% to 95 mol%.

The monomeric subunit m1 may be present in the homopolymer or copolymer in an amount of at least 5mol%, such as at least 20mol%, such as at least 40mol%, based on the total molar concentration of the homopolymer or copolymer, and in some cases, the monomeric subunit m1 may be present in the homopolymer or copolymer in an amount of 100mol%, such as no more than 80mol%, such as no more than 70mol%, based on the total molar concentration of the homopolymer or copolymer. The monomeric subunit m1 may be present in the homopolymer or copolymer in an amount of from 5mol% to 100mol%, such as from 20mol% to 80mol%, such as from 40mol% to 70mol%, based on the total molar concentration of the homopolymer or copolymer.

The homopolymer or copolymer may be free of monomeric subunit m2. If any, the monomeric subunit m2 may be present in the homopolymers or copolymers disclosed herein in an amount of at least 0.1mol%, such as at least 20mol%, such as at least 30mol%, based on the total molar concentration of the homopolymer or copolymer, and in some cases, the monomeric subunit m2 may be present in the homopolymer or copolymer in an amount of 95mol%, such as at least 80mol%, such as at least 30mol%, based on the total molar concentration of the homopolymer or copolymer. The monomeric subunit m2 may be present in the homopolymer or copolymer, if any, in an amount of from 0.1 to 95mol%, such as from 20 to 80mol%, such as from 30 to 60mol%, based on the total molar concentration of the homopolymer or copolymer.

The homopolymer or copolymer, if any, may be present in the conversion coating composition in an amount of at least 100ppm, such as at least 150ppm, such as at least 300ppm, such as at least 400ppm, based on the total weight of the conversion coating composition, and in some cases, the homopolymer or copolymer may be present in the conversion coating composition in an amount of no more than 3000ppm, such as no more than 1000ppm, such as no more than 750ppm, such as no more than 600ppm, based on the total weight of the conversion coating composition. The homopolymer or copolymer, if any, may be present in the conversion coating composition in an amount of 100ppm to 3000ppm, such as 150ppm to 1000ppm, such as 300ppm to 750ppm, such as 400ppm to 600ppm, based on the total weight of the conversion coating composition.

The conversion coating composition and/or conversion coating formed therefrom may further include a group IA metal, a group IIA metal, a group VB metal, a group VIIB metal, and/or a group XII metal. The group IA metal may include lithium. The group IIA metal may include magnesium. The group VB metal may include vanadium. The group VIIB metal may include manganese. The group XII metal can include zinc.

When a continuous or semi-continuous conversion coating is formed on the surface of a substrate, the layer can have a uniform thickness or a variable thickness, that is, the layer can have a different thickness at different locations on the substrate being treated. The average thickness of the conversion coating on the metal surface can be 0.05 mg/square inch (msi) or less, such as 0.001msi to 0.05msi,0.001msi to 0.04msi,0.001msi to 0.03msi,0.001msi to 0.02msi,0.01msi to 0.05msi, or 0.01msi to 0.02msi, or any other combination of ranges using these endpoints. For example, the average thickness of the conversion coating on the metal surface may be 0.05msi,0.04msi,0.02msi,0.01msi,0.005msi, or 0.001msi. The average thickness disclosed herein is determined by removing the conversion coating from a piece of coating can of known area using a known volume of stripping agent, and then measuring the concentration of zirconium in the solution by inductively coupled plasma emission spectroscopy (ICP-OES). The zirconium concentration is then converted to msi (milligrams per square inch) and determined as the thickness of the conversion coating.

The film-forming layer can be deposited from a film-forming composition. Any suitable film-forming composition may be used in accordance with the present invention. As used herein, the term "film-forming composition" refers to a composition that generally includes one or more film-forming resins that can form a self-supporting continuous or semi-continuous film on at least one horizontal surface of a substrate upon removal of any diluents or carriers present in the composition or upon curing at ambient or elevated temperatures. Conventional film-forming resins that can be used include, but are not limited to, those typically used in packaging coating compositions. The film-forming composition may comprise a thermosetting film-forming resin or a thermoplastic film-forming resin. As used herein, the term "thermoset" refers to a resin that "cures" irreversibly upon curing or crosslinking, wherein the polymer chains of the polymeric components are linked together by covalent bonds. This property is typically associated with a crosslinking reaction of the composition ingredients, for example, caused by heat or radiation. The curing or crosslinking reaction may also be carried out at ambient conditions. Once cured or crosslinked, thermoset resins will not melt upon application of heat and are insoluble in solvents. As used herein, the term "thermoplastic" refers to a resin that includes polymer components that are not joined by covalent bonds and thus can undergo liquid flow upon heating and is soluble in a solvent.

Ambient conditions generally refer to room temperature and humidity conditions or temperature and humidity conditions typically found in the area where the composition is applied to a substrate, for example, a temperature between 10 ℃ and 40 ℃, a relative humidity between 5% and 80%, such as a temperature between 20 ℃ and 40 ℃, a relative humidity between 20% and 80%, and an elevated temperature is a temperature above ambient temperature.

The film-forming composition may comprise any of a variety of polymers known in the art. In general, these polymers may be any of these types of polymers prepared by any method known to those skilled in the art. Film-forming compositions can include, for example, acrylic polymers, polyester polymers, phenolic resins, epoxy mimetics, laminates, polyurethane polymers, polyamide polymers, polyvinyl chloride (PVC) resins, alkyd resins, polyether polymers, polysiloxane polymers, and/or copolymers thereof. The film-forming composition may include a phenolic resin, an epoxy resin, a polyester polymer, an acrylic polymer, and/or a polyolefin polymer. The film-forming composition may include an acrylic polymer. The film-forming layer may include phenolic resins, epoxy resins, polyesters, acrylics and/or polyolefins. The film-forming composition may include an emulsion polymerized latex acrylic material, a solution polymerized latex acrylic material, an amine epoxy polymeric material, or a combination thereof. For example, the film-forming composition may include a core-shell acrylic latex.

The functional groups on the film-forming resin may be selected from any of a variety of reactive functional groups: including, for example, carboxylic acid groups, amine groups, epoxy groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including, but not limited to, blocked isocyanate groups), thiol groups, and combinations thereof.

The film-forming layer on the metal can have any suitable dry film thickness. For example, the film-forming layer can have a dry film thickness of greater than 2 micrometers (μm), greater than 5 μm, greater than 10 μm, less than 40 μm, less than 30 μm, less than 20 μm, or a combination of ranges using these endpoints. For example, the dry film thickness may be 2 μm to 40 μm,2 μm to 30 μm,2 μm to 20 μm,5 μm to 40 μm,5 μm to 30 μm,5 μm to 20 μm, and the like. The dry film thickness of the film-forming layer was determined using a SENCON SI9600 coating thickness gauge.

As used herein, "hydrogen sulfide-producing liquid" means a liquid, such as sulfite, that contains at least 1 part per million (ppm) of a sulfur source, in which a reaction between an uncoated metal substrate and the sulfur source produces hydrogen sulfide, prior to deposition into a metal can. For example, the hydrogen sulfide-producing liquid comprises at least 5ppm, at least 7ppm, at least 10ppm, at least 30ppm, at least 50ppm and/or less than 100ppm, less than 70ppm, less than 50ppm of a sulfur source. For example, the hydrogen sulfide-producing liquid includes a sulfur source in the range of 5ppm to 100ppm, such as 7ppm to 70ppm, such as 10ppm to 50ppm, such as 30ppm to 50ppm. One skilled in the art will appreciate that sulfur can be detected using a variety of known methods, including but not limited to ion selective electrodes, gas chromatographs with sulfur chemiluminescence detectors, and/or gas detection tubes. The values herein are provided using the gas detection tube method described herein.

The hydrogen sulfide generating liquid deposited in the metal can may include wine, beer, cider, cocktail, compl, juice, vinegar, liqueur, coconut milk, soft drink, mead, perfume, body spray, or any other liquid in which a reaction between the uncoated metal substrate and a sulfur source generates hydrogen sulfide.

In recent years, there has been a new interest in canning wine. Wine is made from yeast fermented grape juice, occasionally other fruit juices. As part of the process of wine fermentation and treatment control, sulfur dioxide and/or the like, such as metabisulfite, is often added to wine to stabilize the wine against the growth of harmful bacteria and yeasts. Accordingly, the hydrogen sulfide generating liquid deposited in the metal can may include wine. The wine may comprise sparkling wine, red wine, white wine or pink wine.

The present disclosure also provides a metal can comprising a conversion coating deposited on at least a portion of an inner surface of the metal can, wherein the conversion coating is deposited from a conversion coating composition comprising a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally a phosphorus-free monomeric subunit m2; a film-forming layer deposited on at least a portion of the conversion coating; and a hydrogen sulfide generating liquid deposited in the metal can so that the inner surface of the metal can is at least partially in contact with the hydrogen sulfide generating liquid.

The conversion coating composition can include a source of a lanthanide, a group VIB metal, a group IIIB metal, and/or a group IVB metal present in the conversion coating. For example, the group IVB metal in the conversion coating can include zirconium. Suitable sources of zirconium in the conversion coating composition include, but are not limited to, hexafluorozirconic acid, alkali metals and ammonium salts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconyl sulfate, zirconium carboxylates, and/or zirconium hydroxycarboxylates, such as hydrofluorozirconic acid, zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, and/or ammonium zirconium citrate. For example, the source of zirconium in the conversion coating composition can include hexafluorozirconic acid.

The group IVB metal may also be titanium and/or hafnium. Suitable sources of titanium compounds include, but are not limited to, fluorotitanic acid and/or salts thereof. Suitable sources of hafnium compounds include, but are not limited to, hafnium nitrate.

The group VIB metals may include molybdenum and/or chromium. Suitable sources of molybdenum in the conversion coating composition may be present in the form of a salt. Suitable molybdenum salts may comprise sodium molybdate, calcium molybdate, potassium molybdate, ammonium molybdate, molybdenum chloride, molybdenum acetate, molybdenum sulfamate, molybdenum formate, and/or molybdenum lactate. Suitable sources of chromium may comprise chromium (III) and/or chromium (VI).

As noted above, the conversion coating compositions of the present invention may include trivalent chromium cations. The conversion coating composition may also include an anion suitable for forming a salt with the trivalent chromium cation, including, for example, a sulfate, nitrate, acetate, carbonate, hydroxide, or combination thereof.

The conversion coating composition may exclude hexavalent chromium or compounds containing hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic anhydride, dichromates, such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium dichromate, barium dichromate, magnesium dichromate, zinc dichromate, cadmium dichromate, and strontium dichromate. When the conversion coating composition and/or the coating or layer formed therefrom, respectively, is substantially free, or completely free of hexavalent chromium, this includes any form of hexavalent chromium, such as, but not limited to, the hexavalent chromium-containing compounds listed above.

Thus, optionally, in accordance with the present invention, the conversion composition and/or the coating or layer deposited therefrom, respectively, may be substantially free and/or may be completely free of one or more of any of the elements or compounds listed in the preceding paragraph. A conversion coating composition and/or a coating or layer, respectively, formed therefrom that is substantially free of hexavalent chromium or derivatives thereof means that hexavalent chromium or derivatives thereof are not intentionally added, but may be present in trace amounts, such as due to impurities or unavoidable environmental contamination. In other words, the amount of material is so small that it does not affect the properties of the conversion composition; in the case of hexavalent chromium, this may also comprise elements or compounds thereof being present in the conversion composition and/or in the coating or layer respectively formed therefrom at such levels as not to burden the environment. The term "substantially free" means that the conversion coating composition and/or a coating or layer, respectively, formed therefrom contains less than 10ppm, based on the total weight of the composition or layer, respectively, of any or all of the elements or compounds listed in the preceding paragraph, if any. The term "substantially free" means that the conversion coating composition and/or the coating or layer, respectively, formed therefrom contains less than 1ppm of any or all of the elements or compounds listed in the preceding paragraph, if any. The term "completely free" means that the conversion coating composition and/or a coating or layer, respectively, formed therefrom contains less than 1ppb of any or all of the elements or compounds listed in the preceding paragraph, if any.

The conversion coating composition can also include a source of phosphate ions. The source of phosphate ions may include phosphoric acid, such as 75% phosphoric acid, monosodium phosphate, and/or disodium phosphate.

The source of phosphate ions can be present in the conversion coating composition in an amount of from 2ppm to 300ppm, such as from 25ppm to 100ppm, based on the total weight of the ingredients in the conversion coating composition. The conversion coating composition can include a source of phosphate ions present in an amount of 100ppm to 300ppm,100ppm to 200ppm,110ppm to 200ppm,120ppm to 180ppm, or in some cases 140ppm to 180 ppm.

The conversion coating composition may also include a source of free fluorine. As used herein, the term "free fluorine" refers to fluoride ion alone. The source of free fluorine in the conversion coating composition can be derived from the source of the lanthanide, group VIB, group IIIB, and/or group IVB metals used in the conversion coating composition. The source of free fluorine in the conversion coating composition may be derived from a source of a group VIB metal used in the conversion coating composition, such as, for example, hexafluorozirconic acid and/or hexafluorotitanic acid and salts thereof. When the conversion coating composition is applied to at least a portion of the interior surface of a metal can, the fluorine in the hexafluorozirconic acid and/or hexafluorotitanic acid will be free fluorine as the group IVB metal is deposited on the metal substrate of the can, and the free fluorine content of the conversion coating composition will increase over time if not controlled as the metal is treated with the conversion coating composition.

The lanthanide, group VIB metal, group IIIB metal, and/or group IVB metal used in the conversion coating composition for forming the conversion coating can be present in the form of a fluorinated metal ion, e.g., zrF ₆ ^- . When the fluorided metal ions react with the substrate and the components hydrolyze to form oxides, the fluoride ions may be released as free fluorine. As more fluoride ions are released into the bath and the free fluorine content increases, the equilibrium of the deposition reaction begins to move away from oxide formation in the opposite direction of the fluorinated metal ions, in other words, the solubility of this component increases and the formation of the conversion coating film becomes more difficult.

In an example, the source of free fluorine can include one of the group IVB metal compounds described above. In other examples, the source of free fluorine may include compounds other than lanthanides, group VIB metal compounds, group IIIB metal compounds, and/or group IVB metal compounds. The source of free fluorine may include any fluorine-containing compound including monofluorides, bifluorides, fluorine complexes and mixtures thereof known to generate fluoride ions. Non-limiting examples of such sources include 1-IF, NH4F, NFI HF2, naF, and NaHF2. Examples also include ammonium and alkali metal fluorides, acyl fluorides, fluoroboric acid, fluorosilicic acid, fluorotitanic acid and fluorozirconic acid and their ammonium and alkali metal salts and other inorganic fluorides, non-limiting examples of which are: zinc fluoride, zinc aluminum fluoride, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride, and hydrofluoric acid, and other similar materials known to those skilled in the art. Water soluble fluorine compounds can be used to introduce free fluorine. Suitable fluorine compounds include alkali metal fluorides such as sodium fluoride, ammonium fluorides such as ammonium fluoride and ammonium bifluoride, other inorganic fluorides such as sodium fluorosilicate, ammonium fluorosilicate, hydrofluoric acid, hydrofluorosilicic acid such as 23% hydrofluorosilicic acid, and fluoroboric acid such as 50% fluoroboric acid.

Free fluorine may be present in the conversion coating composition in an amount of from 5ppm to 300ppm, such as from 25ppm to 100ppm, based on the total weight of the ingredients in the conversion coating composition. The conversion coating composition can include free fluorine in an amount of 100ppm to 300ppm,100ppm to 200ppm,110ppm to 200ppm,120ppm to 180ppm or, in some cases, 140ppm to 180 ppm. The free fluoride ion may be present in the conversion coating composition in a weight ratio to the group VIB metal, the group IIIB metal, and/or the group IVB metal of 40, in some cases 8:1.

The pH of the conversion coating composition, when applied, may be less than 7, and in some cases, the pH may range between 1 and 6, such as between 1.5 and 5.5. The pH of the conversion coating composition may be maintained by the addition of pH adjusting agents, such as acids and/or bases. Inorganic acids such as hydrofluoric acid, fluoroboric acid and/or phosphoric acid; organic acids such as lactic acid, acetic acid, citric acid, tannic acid and/or sulfamic acid; and/or a water-soluble or water-dispersible base such as sodium hydroxide, ammonium hydroxide, ammonia or an amine such as triethylamine and/or methylethylamine. Inorganic acids such as, for example, sulfuric acid, hydrochloric acid and/or nitric acid may also be used to adjust the pH.

The pH adjusting agent may be present in the conversion coating composition at 0.01% w/w to 10% w/w of the conversion coating. For example, the amounts of acid and/or base may be 0.01% w/w to 9%w/w, 0.01% w/w to 8%w/w, 0.01% w/w to 7%w/w, 0.01% w/w to 6%w/w, 0.01% w/w to 5%w/w, 0.02% w/w to 10% w/w, 0.02% w/w to 9%w/w, 0.02% w/w to 8%w/w, 0.02% w/w to 7%w/w, 0.02% to 8583 z8583/w, 0.02% w/w to 9843 zxft, 0.03% w/w to 3542 zxft 03% w/w, 0.03% w to 35xfw, 0.03% w to 3580 w/w, 0.0.0.02% w to 35xfw/w to 3552 zxft/w, 0.03% w to 3772% w, 0.w to 3580 w/w, 0.5% w to 3724 zxft/w, 0.5% w to 5% w to 3703 w/w, 0.w/w, 0.5% w to 5% w/w, 0.5% w, 0.w/w, 0.5% w to 3703 w/w, 0.5% w, etc.

The conversion coating composition may also include a sequestering agent (sequestrant) and/or a chelating agent, such as, for example, sodium gluconate. The conversion coating composition may also include sodium gluconate to prevent staining of bright aluminum.

The conversion coating composition may also include an electropositive metal. The electropositive metal may include copper, nickel, silver, gold, and combinations thereof. The electropositive metal may include copper. The copper may include copper nitrate, copper sulfate, copper chloride, copper carbonate, or copper fluoride. The electropositive metal may comprise parts per million by weight of greater than 0 to 150 parts per million (ppm), based on the total weight of the ingredients in the conversion coating composition. For example, the electropositive metal may be present in the conversion composition in an amount of at least 2ppm, such as at least 10ppm, such as at least 50ppm, such as at least 75ppm, such as at least 100ppm, and may be present in the conversion composition in an amount of no more than 150ppm, based on the total weight of the ingredients in the conversion coating composition. For example, the electropositive metal can comprise a weight fraction of 2ppm to 150ppm,10ppm to 150ppm,50ppm to 150ppm,75ppm to 150ppm,100ppm to 150ppm, based on the total weight of ingredients in the conversion coating composition.

For example, the conversion coating composition may include hexafluorozirconic acid as a source of group VIB metals and a source of free fluorine, hydrofluorosilicic acid and fluoroboric acid as sources of free fluorine, phosphoric acid as a source of phosphate ions, sodium gluconate as a release agent, nitric acid, ammonia and tannic acid as pH adjusters, and deionized water. In another example, the coating composition can include hexafluorozirconic acid as a source of the group VIB metal, phosphoric acid as a source of phosphate ions, copper nitrate as the electropositive metal, and deionized water.

The present disclosure also relates to a method of packaging a hydrogen sulfide-producing liquid in a metal can, the method comprising depositing the hydrogen sulfide-producing liquid in the metal can, wherein the metal can comprises a conversion coating deposited on at least a portion of an inner surface of the metal can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally a phosphorus-free monomeric subunit m2; and a film-forming layer deposited on at least a portion of the conversion coating.

The conversion coating compositions disclosed herein may be applied to a metal substrate, such as at least a portion of the inner surface of a can body and/or can end of a metal can. The conversion coating composition can be applied to the substrate using any suitable technique, such as brushing, dipping, flow coating, spraying, and the like. However, in some cases, such deposition of the conversion composition may include an electrocoating step, wherein the electrodepositable composition is deposited onto the metal substrate by electrodeposition. For example, the conversion coating composition may be applied as a spray. Suitably, the pump may draw the conversion coating composition from the tank/bath through the spray stand pipe and, after spraying onto the substrate, the excess conversion coating composition drains back into the tank/bath.

After the substrate is contacted with the conversion coating composition, a film-forming composition can be deposited onto at least a portion of the surface of the substrate that has been contacted with the conversion coating composition. Such film-forming compositions can be deposited onto a substrate using any suitable technique, including, for example, brushing, dipping, flow coating, spraying, and the like. However, in some cases, such deposition of the film-forming composition can include an electrocoating step, wherein the electrodepositable composition is deposited onto the metal substrate by electrodeposition. In some other cases, such deposition of the film-forming composition includes a powder coating step. The deposition of the film-forming composition may be a laminate. In still other cases, the film-forming composition can be a liquid coating composition.

The method can further include applying a film-forming composition to form a film-forming layer on at least a portion of the metal can on which the conversion coating composition is deposited. The method can further include applying a coating derived from the film-forming composition to form a film-forming layer on at least a portion of the metal can on which the conversion coating composition is deposited.

The film-forming composition may be cured by any suitable method. The film-forming composition may be cured by thermal curing, radiation curing, or by chemical curing, such as by thermal curing. The film-forming composition can be cured at any suitable temperature upon thermal curing. The film-forming composition, when thermally cured, may be cured to a Peak Metal Temperature (PMT) of 150 to 350 ℃, such as 175 to 320 ℃, such as 190 to 300 ℃, or even 200 to 280 ℃. The film-forming composition may be cured at a temperature of 210 ℃ or 260 ℃ upon thermal curing. Curing the film-forming composition to form the film-forming layer described herein.

The substrate may optionally be subjected to other treatments prior to coating. For example, the substrate may be cleaned, cleaned and deoxidized, positively treated, acid washed, plasma treated, laser treated, or Ion Vapor Deposited (IVD) treated. These optional treatments may be used alone or in combination with the conversion composition.

At least a portion of the surface of the metal substrate may be cleaned and/or deoxygenated and/or otherwise pretreated to remove grease, dirt, and/or other foreign matter using any conventional method of cleaning or pretreating a metal substrate known in the art prior to contacting at least a portion of the surface of the substrate with the conversion coating composition. At least a portion of the substrate surface may be cleaned by physical and/or chemical means, such as mechanically abrading the surface and/or cleaning/degreasing the surface with commercially available alkaline or acidic cleaners well known to those skilled in the art. Examples of acidic cleaners include PCL-452 (a sulfuric acid based surfactant) and ACC45SS (a hydrofluoric acid based), which can be used as a two-part system, each of which is commercially available from PPG Industries (PPG Industries, inc.). Such cleaners are typically used either before or after water washing, such as with tap water, distilled water, deionized water, or combinations thereof.

As described above, at least a portion of the cleaned substrate surface may be mechanically and/or chemically deoxygenated. As used herein, the term "deoxygenation" means the removal of a native oxide layer found on the surface of a substrate to promote uniform deposition of a conversion coating composition and to promote adhesion of a film-forming composition to the surface of the substrate. Suitable oxygen scavengers are familiar to the person skilled in the art. Typical mechanical deoxidizers can be uniformly roughened substrate surfaces, such as by use of a scrubbing or cleaning pad. Typical chemical deoxidizers include, for example, acid-based deoxidizers such as phosphoric acid, nitric acid, fluoroboric acid, sulfuric acid, chromic acid, hydrofluoric acid, and ammonium bifluoride, or the Amchem 7/17 deoxidizer (available from hankel Technologies, madison Heights, MI), the OAKITE deoxidizer LNC (available from Chemetall), TURCO deoxidizer 6 (available from hankel), chemdeox 395 (based on fluorosilicic acid), chemdeox 400 (based on sulfuric acid, fluorosilicic acid, and hydrofluoric acid, and PPG), or combinations thereof. Typically, the chemical oxygen scavenger comprises a carrier, typically an aqueous medium, such that the oxygen scavenger may be in the form of a solution or dispersion in the carrier, in which case the solution or dispersion may be contacted with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, spraying after dipping, dipping after spraying, brushing, or rolling. In accordance with the present invention, when the solution or dispersion is applied to a metal substrate, the skilled artisan will select a temperature range, for example, from 50 ° F to 150 ° F (10 ℃ to 66 ℃), such as from 70 ° F to 130 ° F (21 ℃ to 54 ℃), such as from 80 ° F to 120 ° F (27 ℃ to 49 ℃), based on the corrosion rate. The contact time may be from 30 seconds to 20 minutes, such as from 1 minute to 15 minutes, such as from 90 seconds to 12 minutes, such as from 3 minutes to 9 minutes.

After the cleaning and/or deoxygenation step, the substrate may optionally be rinsed with an aqueous solution of tap water, deionized water, and/or a rinsing agent to remove any residue. The wet substrate surface may be pretreated by any substrate protection method familiar to those skilled in the art, such as anodizing or treating with the conversion coating composition and/or treating with one of the above-described treatment compositions, or drying, such as air drying, the substrate prior to treating the substrate surface, for example, by using an air knife, by flashing off moisture by briefly exposing the substrate to an elevated temperature (e.g., 15 ℃ to 100 ℃, such as 20 ℃ to 90 ℃), or in a heater assembly, for example, using infrared heating, such as heating at 70 ℃ for 10 minutes, or by transferring the substrate between squeeze rolls.

The conversion coating composition and/or film-forming composition may be applied to the metal substrate of the metal can or a portion thereof as part of a single or multi-layer system. The conversion coating composition may be applied as a single layer. The conversion coating composition may be applied as two or more layers. The conversion coating composition may be applied to an uncoated substrate. For the avoidance of doubt, an "uncoated substrate" comprises a surface which is cleaned prior to application. The film-forming composition may be applied as a single layer. The film-forming composition may be applied as two or more layers. The film-forming composition may be applied as part of a multi-layer system on top of another layer. For example, the film-forming composition may be applied on top of a conversion coating top primer. The film-forming composition may form an intermediate layer or a top coat layer. The film-forming composition may be applied as the first coating layer of a multi-coating system. The film-forming composition may be applied as a primer or primer. The second, third, fourth, etc. coating layers may comprise any suitable coating composition, such as, for example, including polyvinyl chloride (PVC) resins, alkyd resins; polyolefin resins, epoxy resins; a polyester resin; a polyurethane resin; a polysiloxane resin; hydrocarbon resins or combinations thereof. The second, third, fourth, etc. coating layers may comprise a polyester resin. The second, third, fourth, etc. coating may be a liquid coating or a powder coating.

The conversion coating composition and/or film-forming composition can be applied to the metal substrate before or after forming the metal can. For example, the conversion coating composition and/or film-forming composition may be applied to a can web and then the tube, can, or can lid (e.g., without limitation, a full aperture easy-open end) is pulled. The conversion coating composition and/or the film-forming composition may be applied to a prefabricated metal can.

The coated metal cans of the present invention can exhibit corrosion resistance, and the hydrogen generating fluid sealed in such metal cans can exhibit a reduction or prevention as compared to metal cans not treated as described herein.

When the hydrogen sulfide generating liquid is deposited in the coated metal can and sealed, the average hydrogen sulfide concentration of the hydrogen sulfide generating liquid is detected to be less than 35ppb, such as less than 20ppb or less than 10ppb, by the gas detection tube method described below, at least 2 months after the can is sealed. The average hydrogen sulfide concentration may be less than 5ppb, or even less than 1ppb, for at least 2 months after the metal can is sealed. When the hydrogen sulfide generating liquid is deposited in the coated metal can andwhen sealed, the hydrogen sulfide generating fluid, when sealed, has an average hydrogen sulfide concentration of less than 35ppb, such as less than 20ppb or less than 10ppb, as measured by the gas detection tube method described below, for at least 3 months, at least 4 months, at least 5 months, at least 6 months, at least 7 months, at least 8 months, at least 9 months, at least 10 months, at least 11 months, or at least 12 months after the can is sealed. As explained below, H disclosed herein ₂ The S concentration was determined by bubbling the wine and measuring the effluent with a gas detector tube (Gastec 4LT, japan) that was previously calibrated for sodium sulfide in wine.

The conversion coating composition and/or the film-forming composition can be substantially free, or can be completely free of styrene. "substantially free" with respect to styrene, based on the total weight of monomers forming the film-forming resin, means that the film-forming resin is formed from monomers comprising less than 5wt% styrene. Substantially free with respect to styrene means that the film-forming resin is formed from monomers comprising less than 1wt% styrene, based on the total weight of the film-forming resin-forming monomers. By completely free with respect to styrene, based on the total weight of the monomers forming the film-forming resin, it is meant that the film-forming resin is formed from monomers comprising less than 0.01wt% styrene. The film-forming resin may be formed from monomers that do not include (i.e., 0 wt.%) styrene, based on the total weight of the monomers that form the film-forming resin.

The conversion coating compositions and/or film-forming compositions of the present disclosure may be substantially free, or may be completely free of bisphenol a (BPA) and derivatives thereof. Derivatives of bisphenol a include, for example, bisphenol a diglycidyl ether (BADGE). The conversion coating and/or film-forming layer of the present disclosure may also be substantially free, may be substantially free, or may be completely free of bisphenol F (BPF) and its derivatives. Derivatives of bisphenol F include, for example, bisphenol F diglycidyl ether (BPFG). The above-mentioned compounds or derivatives thereof may not be intentionally added to the composition but may be present in trace amounts due to unavoidable environmental pollution. By "substantially free" it is meant that the coating composition or component thereof contains less than 1000 parts per million (ppm) of any of the above compounds or derivatives thereof. By "substantially free" it is meant that the coating composition or component thereof contains less than 100ppm of any of the above compounds or derivatives thereof. By "completely free" it is meant that the coating composition or component thereof contains less than 20 parts per billion (ppb) of any of the above compounds or derivatives thereof.

The conversion coating composition and/or the film-forming composition can be substantially free, or can be completely free of formaldehyde. By "substantially free" it is meant that the coating composition or components thereof contain less than 1000 parts per million (ppm) of formaldehyde. By "substantially free" it is meant that the coating composition or a component thereof contains less than 100ppm of any formaldehyde. By "completely free" it is meant that the coating composition or components thereof contain less than 20 parts per billion (ppb) of formaldehyde.

For purposes of the detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, except in any operating examples, or where otherwise indicated, all numbers such as those expressing values, amounts, percentages, ranges, subranges, or fractions, may be read as if prefaced by the word "about", even if the term does not expressly appear. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In the case of closed or open numerical ranges described herein, all numbers, values, amounts, percentages, subranges and fractions within or encompassed by the numerical ranges are to be considered specifically contained in and within the original disclosure of the present application as if such numbers, values, amounts, percentages, subranges and fractions were explicitly written out in their entirety.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

As used herein, the singular encompasses the plural and vice versa unless otherwise specified. For example, while reference is made herein to "a" group VIB metal, "a" film-forming resin, and the like, one or more of each of these and any other components may be used.

As used herein, "comprising," "containing," and similar terms, in the context of this application, are to be understood as synonymous with "including" and thus open-ended and do not exclude the presence of additional unrecited or unrecited elements, materials, ingredients, or method steps. As used herein, "consisting of … …" is understood in the context of this application to exclude the presence of any unspecified elements, ingredients, or method steps. As used herein, "consisting essentially of … …" is understood in the context of this application to include the named elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described.

As used herein, the terms "group IA metal" and "group IA element" refer to elements in group IA of the CAS version of the periodic table of the elements, as shown, for example, in Handbook of Chemistry and Physics, 63 rd edition (1983), which group IA corresponds to group 1 in the actual IUPAC numbering.

As used herein, the term "group IA metal compound" refers to a compound comprising at least one element in group IA of the CAS version of the periodic table of elements.

As used herein, the term "group IIA metal" refers to an element in group IIA of the CAS version of the periodic table of elements, which group IIA corresponds to group 2 in the actual IUPAC numbering, for example as shown in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group IIA metal compound" refers to a compound that includes at least one element in group IIA of the CAS version of the periodic table of elements.

As used herein, the terms "group IIIB metal" and "group IIIB element" refer to elements in group IIIB of the CAS version of the periodic table of the elements, which corresponds to group 3 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group IIIB metal compound" refers to a compound comprising at least one element in group IIIB of the CAS version of the periodic table of elements.

As used herein, the terms "group IVA metal" and "group IVA element" refer to elements in group IVA of the CAS version of the periodic table of the elements, corresponding to group 14 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group IVA metal compound" refers to a compound comprising at least one element in group IVA of the CAS version of the periodic table of the elements.

As used herein, the terms "group IVB metal" and "group IVB element" refer to elements in the group IVB of the CAS version of the periodic table of the elements, which corresponds to group 4 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group IVB metal compound" refers to a compound comprising at least one element in group IVB of the CAS version of the periodic table of elements.

As used herein, the terms "group VB metal" and "group VB element" refer to elements in the group VB of the CAS version of the periodic table of the elements, which corresponds to group 5 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group VB metal compound" refers to a compound comprising at least one element in group VB of the CAS version of the periodic table of elements.

As used herein, the terms "group VIB metal" and "group VIB element" refer to elements in group VIB of the CAS version of the periodic table of the elements, corresponding to group 6 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group VIB metal compound" refers to a compound comprising at least one element in group VIB of the CAS version of the periodic table of elements.

As used herein, the terms "group VIIB metal" and "group VIIB element" refer to elements in group VIIB of the CAS version of the periodic table of the elements, which corresponds to group 7 in the actual IUPAC numbering, as shown, for example, in the handbook of chemistry and physics, 63 rd edition (1983).

As used herein, the term "group VIIB metal compound" refers to a compound comprising at least one element in group VIIB of the CAS version of the periodic table of elements.

In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in some cases.

As used herein, "comprising," "including," and similar terms, are understood in the context of this application to be synonymous with "including" and thus open-ended and do not exclude the presence of additional unrecited or unrecited elements, materials, ingredients, or method steps. As used herein, "consisting of … …" is understood in the context of this application to exclude the presence of any unspecified elements, ingredients, or method steps. As used herein, "consisting essentially of … …" is understood in the context of this application to include the named elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described.

As used herein, the terms "over … …", "onto … …", "applied over … …", "applied over … …", "formed over … …", "deposited over … …", "deposited over … …" mean formed, covered, deposited or provided on but not necessarily in contact with the surface. For example, a film-forming composition "deposited onto" a substrate does not preclude the presence of one or more other intermediate coatings of the same or different composition positioned between the film-forming composition and the substrate.

As used herein, "salt" refers to an ionic compound composed of a cation and an anion and having an overall charge of zero. The salt may be hydrated or anhydrous.

As used herein, "composition" refers to a solution, mixture, or dispersion in a medium.

As used herein, "coating composition" refers to a composition that is capable of producing a film, layer, etc., on at least a portion of the surface of a substrate in an at least partially dried or cured state.

As used herein, the term "dispersion" refers to a two-phase transparent, translucent, or opaque system in which the particles are in the dispersed phase and the aqueous medium comprising water is in the continuous phase.

As used herein, "deoxidizing composition" refers to a composition having a pH of no greater than 3.0 and a free fluorine content of no greater than 50ppm, based on the total weight of the deoxidizing composition, and that is capable of etching and/or reacting with and chemically modifying a substrate surface.

As used herein, "deoxygenating composition bath" or "deoxygenating bath" refers to an aqueous bath that contains a deoxygenating composition and may contain components that are byproducts of the process.

As used herein, "detergent composition" refers to a composition that removes oil, soil, and other contaminants from a substrate surface and is optionally capable of etching or oxidizing the substrate surface.

As used herein, "detergent composition bath" refers to an aqueous bath that contains a detergent composition and may contain components that are byproducts of the process.

As used herein, "pretreatment composition" refers to a composition that is capable of reacting with and chemically altering the surface of a substrate and combining therewith to form a film that provides corrosion protection.

As used herein, "pretreatment bath" refers to an aqueous bath that contains a conversion composition and may contain components that are byproducts of the process.

Also, the recitation of numerical ranges by endpoints includes all integers and, where appropriate, fractions within that range (e.g., 1 to 5 can include 1, 2, 3, 4 when referring to, for example, multiple elements, and can also include 1.5, 2, 2.75, and 3.80 when referring to, for example, measurements). Recitation of endpoints also includes the endpoint values themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

As used herein, the term "cure" means that the components forming the composition crosslink to form a film, layer, or bond. As used herein, the term "at least partially cure" means that at least a portion of the components forming the composition interact, react, and/or crosslink to form a film, layer, or bond.

As used herein, the terms "comprising," "comprises," and "comprising" are synonymous with "including," or "containing," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps. Additionally, while the present invention has been described with "comprising," the coating compositions detailed herein may also be described as "consisting essentially of … …" or "consisting of … …".

As used herein, the term "and/or," when used in a list of two or more items, means that any one of the listed items can be used alone, or any combination of two or more of the listed items can be used. For example, if a list is described as including groups A, B and/or C, the list may include individual a; b alone; c alone; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B and C.

As used herein, the term "polymer" broadly refers to prepolymers, oligomers, and both homopolymers and copolymers. It should be noted that the prefix "poly" refers to two or more.

While specific embodiments of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Aspect(s)

In view of the foregoing, the present invention therefore particularly relates to, but is not limited to, the following:

aspect 1. A metal can, comprising

A conversion coating deposited on at least a portion of the inner surface of the metallic can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2;

a film-forming layer deposited on at least a portion of the conversion coating; and

a hydrogen sulfide generation liquid deposited in the canister.

Aspect 2 the metal can of aspect 1, wherein the metal can comprises aluminum, aluminum alloy, and/or steel.

Aspect 3 the metal can of aspect 2, wherein the metal can comprises an aluminum alloy.

Aspect 4. The metal can of any of the above aspects, wherein the lanthanide element comprises lanthanum and/or cerium, the group VIB metal comprises chromium and/or molybdenum, the group IIIB metal comprises yttrium, and the group IVB metal comprises zirconium, titanium, and/or hafnium.

Aspect 5. The metal can of any of the above aspects, wherein the group IVB metal comprises zirconium.

Aspect 6. The metal can of aspect 4, wherein the chromium comprises chromium (III) and/or chromium (VI).

Aspect 7 the metal can of any one of the above aspects, wherein the hydrogen sulfide producing liquid comprises wine, beer, juice, vinegar, liqueur, coconut milk, soft drink, cider, comptea or mead.

Aspect 8 the metal can of any one of the above aspects, wherein the conversion coating has an average thickness of 0.001msi to 0.05msi as measured by ICP-OES.

Aspect 9. The metal can of any of the above aspects, wherein the film-forming layer comprises an acrylic, polyester, phenolic, polyolefin, and/or epoxy resin.

Aspect 10 the metal can of any of the above aspects, wherein the film-forming layer comprises an emulsion polymerized acrylic latex.

Aspect 11 the metal can of any of the above aspects, wherein the film-forming layer has a dry film thickness of 2 to 20 micrometers as measured with a SENCON SI9600 coating thickness gauge.

Aspect 12. The metal can of any of the above aspects, wherein the conversion coating is on at least a portion of the can body of the metal can.

Aspect 13. The metal can of any of the above aspects, wherein the conversion coating is on at least a portion of a can end of the metal can.

Aspect 14. A metal can, comprising

A conversion coating deposited on at least a portion of the inner surface of the metallic can, wherein the conversion coating is deposited from a conversion coating composition comprising a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally a phosphorus-free monomeric subunit m2;

and hydrogen sulfide generation liquid in the metal tank.

Aspect 15 the metal can of aspect 14, wherein the metal can comprises aluminum, an aluminum alloy, and/or steel.

Aspect 16 the metal can of aspect 15, wherein the metal can comprises an aluminum alloy.

Aspect 17. The metal can of aspects 14 to 16, wherein the group IVB metal comprises hexafluorozirconic acid.

Aspect 18. The metal can of aspects 14-17, wherein the conversion coating composition further comprises a source of phosphate ions.

Aspect 19. The metal can of aspect 18, wherein the source of phosphate ions comprises phosphoric acid.

Aspect 20. The metal can of aspect 18 or 19, wherein the source of phosphate ions is in an amount of 2ppm to 300ppm.

Aspect 21. The metal can of aspects 14-20, wherein the conversion coating composition further comprises a source of free fluorine.

Aspect 22. The metal can of aspect 21, wherein the source of free fluorine comprises hydrofluorosilicic acid and fluoroboric acid.

Aspect 23. The metal can of aspect 21 or 22, wherein the source of free fluorine is in an amount of 5ppm to 300ppm.

Aspect 24. The metal can of aspects 14 to 23, wherein the group IVB metal comprises a source of free fluorine.

Aspect 25. The metal can of aspects 14 to 24, wherein the conversion coating composition further comprises an electropositive metal.

Aspect 26. The metal can of aspect 25, wherein the electropositive metal is in an amount of 2ppm to 150ppm based on the total weight of the ingredients in the conversion coating composition.

Aspect 27. The metal can of aspect 25 or 26, wherein the electropositive metal comprises copper nitrate.

Aspect 28. A method of packaging a hydrogen sulfide producing liquid in a metal can, the method comprising

Depositing the hydrogen sulfide generating solution in the metal can,

wherein the metal can comprises

A conversion coating deposited on at least a portion of the inner surface of the metallic can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, and/or a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2; and

a film-forming layer deposited on at least a portion of the conversion coating.

Aspect 29. The method of aspect 28, wherein the conversion coating is deposited from a conversion coating composition comprising the lanthanide, the group VIB metal, the group IIIB metal, the group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2.

Aspect 30. The method of aspect 29, wherein the conversion coating composition comprises an electropositive metal, a source of phosphate ions, and/or a source of free fluorine.

Aspect 31 the method of aspect 29, wherein the group IVB metal comprises hexafluorozirconic acid.

Aspect 32 the method of aspect 30, wherein the source of phosphate ions comprises phosphoric acid.

Aspect 33. The method of aspect 30 or 32, wherein the source of phosphate ions is in an amount of 2ppm to 300ppm.

Aspect 34. The method of aspect 30, wherein the source of free fluorine comprises hydrofluorosilicic acid and fluoroboric acid.

Aspect 35. The method of aspect 30 or 34, wherein the source of free fluorine is in an amount of 5ppm to 300ppm.

Aspect 36. The method of aspects 28 to 35, wherein the group IVB metal comprises a source of free fluorine.

Aspect 37. The method of aspect 30, wherein the electropositive metal is present in an amount of 2ppm to 150ppm based on the total weight of the ingredients in the conversion coating composition.

Aspect 38 the method of aspect 30 or 37, wherein the electropositive metal comprises copper nitrate.

Aspect 39. A metal can, comprising

A conversion coating deposited on at least a portion of the inner surface of the metallic can, the conversion coating comprising a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2;

a hydrogen sulfide generating liquid inside the metal can, wherein the hydrogen sulfide concentration of the hydrogen sulfide generating liquid as measured with a gas detection tube is less than 35ppb for at least two months after the metal can is sealed.

Aspect 40. The metal can of aspect 39, wherein the metal can comprises aluminum, an aluminum alloy, and/or steel.

Aspect 41. The metal can of aspect 40, wherein the metal can comprises an aluminum alloy.

Aspect 42. The metal can of aspects 39-41, wherein the lanthanide element comprises lanthanum and/or cerium, the group VIB metal comprises chromium and/or molybdenum, the group IIIB metal comprises yttrium, and the group IVB metal comprises zirconium, titanium, and/or hafnium.

Aspect 43. The metal can of aspects 39-42, wherein the group IVB metal comprises zirconium.

Aspect 44. The metal can of aspect 42, wherein the chromium comprises chromium (III) and/or chromium (VI).

Aspect 45 the metal can of aspects 39-44, wherein the hydrogen sulfide producing liquid deposited within the metal can comprises wine, beer, fruit juice, vinegar, liqueur, coconut milk, soft drink, cider, conpu tea, or mead.

Aspect 46. The metal can of aspects 39-45, wherein the conversion coating has an average thickness on the metal can of 0.001msi to 0.05msi as measured by ICP-OES.

Aspect 47. The metal can of aspects 39-46, wherein the film-forming layer comprises an acrylic, polyester, phenolic, polyolefin, and/or epoxy resin.

Aspect 48 the metal can of aspects 39-47, wherein the film-forming layer has a thickness of 1msi to 4msi as measured with a SENCON SI9600 coating thickness gauge.

Aspect 49 the metal can of aspects 39-48, wherein the conversion coating is on at least a portion of the can body of the metal can.

Aspect 50 the metal can of aspects 39-49, wherein the conversion coating is on at least a portion of the can end of the metal can.

Aspect 51. A treatment system for a metal can for packaging a hydrogen sulfide generating liquid, the system comprising

A conversion coating deposited on at least a portion of the inner surface of the metallic can, wherein the conversion coating comprises a lanthanide, a group VIB metal, a group IIIB metal, a group IVB metal, and/or a homopolymer or copolymer comprising a phosphorus-containing monomeric subunit m1 and optionally no phosphorus monomeric subunit m2; and

a film-forming layer deposited on at least a portion of the conversion coating.

Aspect 52. The metal can of aspect 51, wherein the metal can comprises aluminum, an aluminum alloy, and/or steel.

Aspect 53 the metal can of aspect 52, wherein the metal can comprises an aluminum alloy.

Aspect 54. The metal can of aspects 51-53, wherein the metal can further comprises a hydrogen sulfide generating liquid deposited within the metal can.

Aspect 55 the metal can of aspects 51-54, wherein the conversion coating comprises zirconium.

Aspect 56. The metal can of aspect 51, wherein the chromium comprises chromium (III) and/or chromium (VI).

Aspect 57 the metal can of aspects 54-56, wherein the hydrogen sulfide producing liquid deposited within the metal can comprises wine, beer, juice, vinegar, liqueur, coconut milk, soft drink, cider, conpu tea, or mead.

Aspect 58. The metal can of aspects 51-57, wherein the conversion coating has an average thickness on the metal can of 0.001msi to 0.05msi as measured by ICP-OES.

Aspect 59. The metal can of aspects 51-58, wherein the film-forming layer comprises acrylic, polyester, phenolic, polyolefin, and/or epoxy.

Aspect 60 the metal can of aspects 51-59, wherein the film-forming layer has a thickness of 1msi to 4msi as measured by a SENCON SI9600 coating thickness gauge.

Aspect 61. The metal can of aspects 51-60, wherein the conversion coating is on at least a portion of the can body of the metal can.

Aspect 62. The metal can of aspects 51-61, wherein the conversion coating is on at least a portion of the can end of the metal can.

All of the features contained herein may be combined in any combination with any of the above aspects.

For a better understanding of the present invention, and to show how embodiments of the same may be carried into effect, reference will now be made, by way of example, to the following examples.

Examples of the invention

Example 1: zirconium-based conversion coating

Panel preparation

Two sets of aluminum plates (unstretched can body sheet) were cleaned with isopropyl alcohol to remove any manufacturing oil. Then, a set of panels was subjected to zirconium pretreatment according to the order in table 2 (table 1). The aluminum substrate was placed on a rack system and passed to a first stage which contained an array of impingement nozzles spraying alkaline etchant and 2K packaged surfactant cleaner (available from PPG industries, DR1369M and DR 1700).

The panel then enters stage 2, a low pH acid rinse is performed via the bank of overflow nozzles to remove the alkaline etchant, followed by a stage 3 tap water rinse to remove the acid.

Next, in stage 4, the acidic zirconium conversion coating composition shown in Table 1 was sprayed using a hollow cone nozzle to deposit a thin layer of zirconium hydroxide on the surface of the panel. Finally, in stage 5, the panel was rinsed with deionized water and then dried with an Infrared (IR) heater.

The second set of panels did not undergo any pre-treatment. The PPG industry company was then branded PPG using the 20-numbered spindle pull down wet coating

2012-823 markets a commercial interior varnish, acrylic latex paint, applied to both sets of panels. The coated substrate panel was baked at 193 ℃ for three minutes. The nominal thickness of the cured film was measured to be 4-5mg/in2 using a SENCON SI9600 coating thickness gauge.

₂ HS Generation test

The prepared panels were placed in a Sieg-mi-flex extraction cell (LABC-Labortechnik, germany) to a size of 1dm ² Was contacted with 100mL of wine and tested for H production in wine ₂ The case of S gas. The cell was then filled with wine (pH 3.3) (sold by Barefoot Cellars under the trade name Barefoot Cellars)

Crisp White Spritzer, usa) was added with 50ppm sodium metabisulfite and stored in a hot chamber at 50 ℃ for 10 days (representing 2 to 3 months at room temperature). After 10 days, the cell was removed from the hot chamber, cooled to room temperature, and then H was determined by bubbling wine and measuring the effluent with a gas detection tube (Gastec 4LT, japan) ₂ S concentration, the gas detection tube was previously calibrated for sodium sulfide in wine. Wine H in contact with pretreated panel after three replicates of the sample ₂ Average concentration of S23 ppb, H in wine in contact with non-pretreated face sheet ₂ The concentration of S was 40ppb.

Table 1: zr conversion coating composition

Table 2: conditions of pretreatment application

Attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

The invention is not restricted to the details of the above-described embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

1. A metal can, comprising

a hydrogen sulfide generation liquid deposited in the canister.

2. The metal can of claim 1, wherein the metal can comprises aluminum, aluminum alloy, and/or steel.

3. The metallic can of claim 1, wherein said homopolymer or copolymer comprising phosphorus-containing monomeric subunit m1 and optionally non-phosphorus-containing monomeric subunit m2 comprises a homopolymer, a dimer, and/or a trimer, said lanthanide comprises lanthanum and/or cerium, said group VIB metal comprises chromium and/or molybdenum, group IIIB metal comprises yttrium, and said group IVB metal comprises zirconium, titanium, and/or hafnium.

4. The metallic can of claim 1, wherein said group IVB metal comprises zirconium.

5. A metallic can according to claim 3, wherein said chromium comprises chromium (III) and/or chromium (VI).

6. The metal can of claim 1, wherein the hydrogen sulfide producing liquid deposited within the metal can comprises wine, beer, juice, vinegar, liqueur, coconut milk, soft drinks, cider, comper tea, or mead.

7. A metal can according to claim 1, wherein the conversion coating has an average thickness of from 0.001msi to 0.05msi on the metal can.

8. The metal can of claim 1, wherein the film-forming layer comprises an acrylic, polyester, phenolic, polyolefin, and/or epoxy resin.

9. The metal can of claim 1, wherein the dry film thickness of the film-forming layer is from 2 microns to 20 microns.

10. The metal can of claim 1, wherein said conversion coating is on at least a portion of a can body of said metal can.

11. The metal can of claim 1, wherein the conversion coating is on at least a portion of a can end of the metal can.

12. A metal can, comprising

and hydrogen sulfide generation liquid in the metal tank.

13. The metallic can of claim 12, wherein the group IVB metal is hexafluorozirconic acid.

14. The metal can of claim 12, wherein said conversion coating composition further comprises a source of phosphate ions.

15. The metal can of claim 14, wherein said source of phosphate ions comprises phosphoric acid.

16. The metallic can of claim 12, wherein said conversion coating composition further comprises a source of free fluorine.

17. The metal can of claim 12, wherein the conversion coating composition further comprises an electropositive metal.

18. The metal can of claim 12, wherein the group IVB metal in the conversion coating composition comprises a source of free fluorine.

19. A method of packaging a hydrogen sulfide producing liquid in a metal can, the method comprising

Depositing the hydrogen sulfide generating solution in the metal can,

wherein the metal can comprises

a film-forming layer deposited on at least a portion of the conversion coating.

20. A metal can, comprising